Chemically derivatized maltodextrins

ABSTRACT

High solids maltodextrin syrups, some of which are useful as the base for remoistenable adhesives, are prepared by a high solids alpha amylase enzyme conversion process. They are characterized by their high solids content (at least 55 wt. %) and light color. A granular chemically derivatized, optionally converted, starch having a degree of substitution of greater than about 0.01 and less than about 0.5 is used as the starting material. The maltodextrins have a reducing sugar content of about 5-19 dextrose equivalent and a distinct polymodal molecular weight distribution. When a granular highly esterified starch (D.S. of 0.5-1.8) is used as the starting material in the high solids process, the resulting enzyme-converted, esterified maltodextrins are characterized by their improved water dispersibility.

BACKGROUND OF THE INVENTION

In its broadest sense, the term "dextrin" covers any starch degradationproducts, with the exceptions of mono- and oligosaccharides, regardlessof how the starches are degraded. All dextrins belong to a large andvaried group of D-glucose polymers which can be linear, highly branched,or cyclic. Their complexity creates problems in any classification basedon their chemical character. Hence, they are often classified based onhow they are prepared.

The hydrolytic procedures used for their preparation fall into fourmajor groups: products obtained by hydrolysis of dispersed starch by theaction of liquefying enzymes such as amylases; products obtained by theacid hydrolysis of dispersed starch; Schardinger dextrins formed fromdispersed starch by the action of Bacillus macerans transglycosylase;and pyrodextrins produced by the action of heat or heat and acid on drystarch.

Maltodextrins include enzyme- and/or acid-converted dextrins, defined bythe Food and Drug Administration (FDA) as non-sweet, nutritivesaccharide polymers which consist of D-glucose units linked primarily byalpha-1→4 glucosidic bonds and which have a dextrose equivalent (DE) ofless than 20. Corn syrup solids are defined by the FDA as dried glucosesyrups in which the reducing sugar content is 20 DE or higher. Thedegree of hydrolysis strongly affects the functional properties ofmaltodextrins and corn syrup solids.

Manufacturing processes for preparing maltodextrins include single-stageand dual-stage starch slurry processes using acid and/or enzyme. Asolids content of about 18-35% is considered high solids.

A single-stage process combines either acid or enzyme conversion atrelatively high temperatures with gelatinization of the starch. Thehydrolysis may then be continued in hold tanks until the appropriate DEis reached, at which point the hydrolysis is terminated by either pHadjustment or heat deactivation. The product may then be refined orpurified, concentrated and spray-dried.

A dual-stage process involves first a high temperature (usually>105° C.)gelatinization/liquefaction with either acid or enzyme to a low DE(usually<3) followed by a high temperature treatment (as in a jetcooker) to ensure gelatinization of the starch. After pH adjustment andlowering of the temperature to around 82°-105° C., a second conversionstep, usually with a bacterial alpha-amylase, is conducted until thedesired DE is achieved. The enzyme is then deactivated and the productmay then be refined and spray-dried.

Some of the patents covering acid- and/or enzyme-conversion of starchesto maltodextrins are discussed below.

U.S. Pat. No. 2,609.326 (issued Sep. 2, 1952 to W. W. Pigman et al.)discloses rapidly gelatinizing and dispersing starch granules in hotwater while subjecting the starch to intense agitation and shearing,immediately converting the gelatinized and dispersed starch at anelevated temperature with a starch-liquefying amylase characterized byits ability to hydrolyze the starch molecules into large fragments,inactivating the enzyme, and immediately drying the enzyme convertedstarch. The dry cold water dispersible converted starches arecharacterized by a very low content of reducing sugars (3% or less).

U.S. Pat. No. 3,560,343 (issued Feb. 2, 1971 to F. C. Armbruster et al.)discloses a process where a starch is acid hydrolyzed to a D.E. lessthan 15 and then converted with a bacterial alpha-amylase to a DEbetween 10 and 25.

Japanese 46-14706 (published Apr. 20, 1971) discloses a continuousprocess for preparing a granular converted starch which swells, but doesnot dissolve in cold water, and which is reduced in viscosity. A starchalpha amylase mixture having a water content of 40-60%, containingbuffer to adjust the pH to 5-7, is cured for several hours at roomtemperature, or a temperature at or below the gelatinizationtemperature, after which it is put into a starch dryer maintained at70°≅150° C. During the drying, the temperature and water content changeto those suitable for hydrolyzing the starch. The hydrolysis, drying ofthe hydrolyzed starch, and deactivation of the residual enzymesimultaneously occur during the heating at 70°-150° C. Aliquefaction-type amylase shows the strongest hydrolytic activity at70-90° C., but at higher temperatures (i.e., above 90° C.), if themoisture content is above 35%, the starch undergoes the hydrolyticactivity but is gelatinized at the same time and if the water content ofthe mixture is less than 30%, it becomes more difficult to gelatinizethe starch, but at the same time the hydrolysis by the enzyme shows atendency to fall off rapidly. To satisfy these opposing tendencies, itis necessary to reduce the water content of the mixture from 40-60% to30-35% in the dryer and to increase the temperature to 90°-100° C.during the enzyme hydrolysis.

U.S. Pat. No. 3,849,194 (issued Nov. 19, 1974 to F. C. Armbruster)discloses treating a waxy starch with a bacterial alpha-amylase at atemperature above 85° C. to liquify the waxy starch, cooling theliquified waxy starch to about 80° C., and converting the liquified waxystarch with the bacterial alpha-amylase to a D.E. of from about 5 toabout 25.

U.S. Pat. No. 3,663,369 (issued May 16, 1972 to A. L. Morehouse et al.)discloses a two-stage hydrolysis. The first stage is carried out withacids or enzymes at elevated temperatures for short periods to liquifythe starch with very little dextrinization or saccharification. Thesecond stage is carried out at an alkaline pH with bacterialalpha-amylase to achieve the desired D.E.

U.S. Pat. No. 3,853,706 (issued Dec. 10, 1974 to F. C. Armbruster)discloses hydrolyzing starch with a bacterial alpha-amylase to a DE ofless than 15, terminating the hydrolysis by heat treatment, and furtherconverting to a DE of between about 5 and 20.

U.S. Pat. No. 3,974,034 (issued Aug. 10, 1976 to H. E. Horn) disclosesmaltodextrins which are prepared by the enzymatic hydrolysis of anoxidized starch. The starch is first simultaneously liquefied andoxidized at elevated temperatures and then converted with a bacterialalpha amylase to a D.E. not substantially above 20.

U.S. Pat. No. 4,014,743 (issued Mar. 29, 1977 to W. C. Black) disclosesa method for the continuous enzyme liquefication of starch. Preferably,the starch is a raw starch, but pregelatinized or modified starches maybe used (see Column 6, lines 1-7). A suitable enzyme is bacterial alphaamylase. An enzyme-containing suspension of raw starch (10-45 wt. % on adry solids basis) is continuously added to an agitated body of heated(77°-99° C.-170°-210° F.) converted starch. The incoming starch isgelatinized and mixed with the partially converted starch to maintain ablend having a viscosity low enough to be readily agitated and pumped. Astream of the blend is continuously removed from the conversion tank andtreated to inactivate the enzyme. The process is controlled to limit themaximum viscosity of the blend to a Brookfield viscosity of not over5000 cps (100 rpm and 88° C.-190° F.). The reducing sugar content isusually less than 3% on a dextrose equivalent basis. A blend of starchesthat have been subjected to different degrees of enzyme conversion isobtained since the heating and enzyme treatment is not uniform for theindividual starch granules or molecules.

U.K. 1,406,508 (published Sep. 17, 1975) discloses a continuous processfor liquefying natural or chemically modified starch to give starchpastes having a solid content of up to 70% by weight. The starch ingranular form, without the intermediate formation of a slurry, iscontinuously supplied to a reaction zone where it is subjected to theaction of an enzyme (e.g., alpha amylase) in a stirred aqueous medium atan elevated temperature (50°-98° C.) and pH of 4.5-8. Once theliquefaction is completed the liquefied starch is stabilized bydeactivating the enzyme. A greater proportion of large molecules and abroader molecular weight distribution results as compared to adiscontinuous process where the molecules are smaller and substantiallythe same size.

DE 37 31 293 A1 (laid open Apr. 8, 1980) discloses a process forcontinuously degrading and digesting starch. A dry starch powdertogether with liquid water or an aqueous starch suspension is charged toa stirred converter containing a starch degrading enzyme, preferablyalpha amylase, while the temperature is increased to 70°-90° C. by theinjection of steam at 120°-125° C. and 2-4 bar. The product leaving theconverter is treated with an enzyme deactivating agent before finaldilution to the desired concentration.

U.S. Pat. No. 4,921,795 (issued May 1, 1990) to F. A. Bozich, Jr.)discloses an improved slurry method for producing dextrin adhesivesusing alpha amylase in combination with glucoamylase. The function ofthe glucoamylase is to eliminate the limit dextrin problem and themechanical shearing step. The alpha amylase randomly cleaves the α(1→4)linkages of the linear amylose molecules and cleaves the branchedamylopectin molecules up to the (1→6) glucosidic linkages of the limitdextrin. The slurry is stirred sufficiently to create a vortex in theaqueous reaction slurry, thereby maintaining adequate mixing withoutshearing. The hydrolysis is allowed to continue until an optimal mix offragment sizes is achieved (as indicated by a Brookfield viscosity of1000-2000 cps at 20 rpm, 110° F., 45-55% solids, and 0 to 16% sodiumborate pentahydrate). The enzyme is then inactivated. The Theologicalproperties of the resultant slurry can be adjusted as needed.

There is a need for high solids, stabilized (i.e., chemicallyderivatized) maltodextrins which can be used where pyrodextrins ormaltodextrins are conventionally used, for example in remoistenableadhesives.

SUMMARY OF THE INVENTION

The present invention is directed to a clear, off-white to beigemaltodextrin syrup having a solids content of at least 55% by weight,which is prepared from a chemically derivatized converted ornon-converted granular starch. The maltodextrin has (i) substituents inan amount sufficient to provide a degree of substitution greater thanabout 0.01 and less than about 0.5, preferably between 0.05 and about0.17; (ii) a reducing sugar content of between about 5 and about 19dextrose equivalents, preferably between about 10 and about 17; and(iii) a polymodal molecular weight distribution having one peak betweenabout 630 to about 1600 Daltons and at least one other peak betweenabout 1600 and about 2,500,000 daltons, preferably peak(s) between about1600 and about 160,000 daltons.

The chemically derivatized maltodextrin may be prepared from any cereal,tuber, root, legume, or fruit starch.

Typical substituents include ester and/or ether groups and cationicgroups such as diethylaminoethyl chloride hydrochloride or3-chloro-2-hydroxypropyl trimethyl ammonium chloride groups. Suitableether groups include hydroxyethyl, hydroxypropyl, or like hydroxyalkylgroups. Suitable ester groups include acetate, propionate, butyrate,hexanoate, benzoate, and octenylsuccinate groups and mixed starch esterssuch as acetate/propionate, acetate/butyrate and the like. Slightlycrosslinked starches which contain mono-functional ether and/or estersubstituents are also useful herein and can be converted by the processdescribed below.

The high solids maltodextrin syrups are prepared by a high solids enzymeconversion process which comprises the steps of:

a) adding, to chemically derivatized starch having a degree ofsubstitution of about 0.01 to about 0.50, an alpha amylase enzyme andwater in an amount sufficient to produce a single phase powdered mixturewithout a visible free water phase;

b) activating the enzyme by heating the powdered mixture to about theoptimum temperature for the enzyme while maintaining a substantiallyconstant moisture content (i.e., ±5% of the starting moisture content)in the mixture;

c) allowing the enzyme to hydrolyze the starch to a degree sufficient togive a chemically derivatized maltodextrin syrup having a reducing sugarcontent of between about 5 and about 19, preferably between about 10 andabout 17; and

d) preferably inactivating the enzyme after the desired dextroseequivalent is reached.

In step (d) the solids content may be reduced by adding water.

Optionally, the water can be removed from the aqueous maltodextrin syrupand the maltodextrin recovered as a powdered chemically derivatizedmaltodextrin.

The present invention is also directed to enzyme-converted, highlyesterified starch esters having a degree of substitution of about 0.5 toabout 1.8 which are characterized by their self emulsifying propertiesin water. Preferably, the starch esters are highly acetylated waxy maizeor corn starch esters having a degree of substitution (D.S.) of about 1to about 1.25. The starch esters are prepared by adding, to a coldwater-insoluble starch ester having a degree of substitution of about0.5 to about 1.8, an alpha amylase enzyme and water in an amountsufficient to produce a powdered mixture without a visible free waterphase and allowing the alpha amylase to hydrolyze and liquefy thestarch. The alpha amylase may be mixed with a beta amylase or aglucoamylase.

A suitable method for preparing the starch esters is described in U.S.Pat. No. 5,321,132 (issued Jun. 14, 1994 to R. L. Billmers et al.), thedisclosure of which is incorporated herein by reference. The starchesters have the formula ##STR1## where St is the starch base and R andR' are different and are selected from the group consisting of alkyl,aryl, alkenyl, alkaryl, and aralkyl groups having 1 to 7 carbon atoms.Starch esters of this type include the acetate, propionate, butyrate,hexanoate, benzoate, and mixed esters such as the acetate/propionate.The granular base starch may be any of the native starches describedhereafter or may be any of the chemically and/or physically modifiedstarches disclosed in the '132 patent.

The esters are prepared by reacting a granular starch with a sufficientamount of an organic anhydride to obtain the desired D.S. Typically,from about 35-300%, preferably 50-200%, by weight, of anhydride is usedbased on the dry weight of the starch. The reaction is carried out in anaqueous medium at a pH of about 7-11, preferably 7.5-10, and atemperature of about 0°-40° C., preferably 5°-20C. Because of the largeamount of anhydride required, it is desirable to use a concentratedamount of aqueous alkali, e.g., about 10-50%, preferable 20-30%, byweight. Any alkali is suitable. Preferred alkalies are the alkali metalhydroxides, most preferably sodium hydroxide.

As will be shown in the examples, when a starch ester, e.g., theacetate, is converted by the high solids, single phase enzyme conversionprocess, the original non-water-dispersible starch ester becomes readilydispersible in water at room temperature after the enzyme conversion.The significant reduction in viscosity indicates that the highlysubstituted starch is hydrolyzed even though chemical substituentstypically interfere with enzyme conversion. The hydrolyzed starch stillretains a high degree of substitution. The GPC molecular weight profileshows multiple peaks. As used herein, "starch" is intended to includenon-pregelatinized granular starches, pregelatinized granular starches,and starches which are pregelatinized but not cold-water-soluble.

As used herein, "single phase" means a mixture which has no visible freewater, whereas a "slurry" consists of two phases, i.e., a water phaseand a starch phase. The preferred total water content herein is about 15to 40% by weight of the total mixture, except when a converted granularstarch is being prepared with only alpha amylase where the total watercontent is about 15-35%.

The powdered or preferably liquid enzyme and sufficient water to givethe desired total moisture content are dispersed onto a granular starchpowder. The typical moisture content of granular starches is about10-14%. Thus, sufficient water is added in step (a) to bring the totalamount of water to the desired amount. As used herein, the term "totalamount of water" refers to the total of the equilibrium moisturetypically present in a granular starch and the added water.

If the moist single phase powdered mixture is subjected to a mixingprocess which kneads and compacts, such as that typical of dough mixingequipment or viscous polymer compounding equipment, it may, dependingupon the water content and amount of solubles present, become a veryhigh viscosity compact doughy mass before the onset of gelatinizationand conversion. Continued mechanical shearing will raise the temperatureand cause gelatinization and conversion.

When the powdered starch mixture contains a granular starch, as thepowdered mixture is heated, the heat and moisture initiate the swellingof the starch granules and the starch is completely or partiallygelatinized and simultaneously converted. When the powdered mixturecontains a pregelatinized, non-cold-water-dispersible starch, the heatand moisture disperse the starch and the starch is fully gelatinized andsimultaneously converted. As the starch is converted, usually the powderliquefies. The peak viscosity of the native starch is never reached.

The maltodextrin may be in the form of a syrup, a converted granularstarch, or a mixture of the syrup and the converted granular starch. Asused herein, "syrup" covers liquids and viscous pastes. The resultingstarch syrup is obtained at a high solids content (e.g., at least 60%,typically 65-75% by weight). The syrup may be spray dried, belt-dried,or freeze dried. The enzyme-converted starch may be recovered from thestarch syrup as a water-soluble powder. If desired, the sugarby-products may be removed from the granular converted starch bywashing.

Optionally, an enzyme activator such as certain inorganic salts and/or apH adjuster such as an acid, a base, or a buffer may be used.

The enzyme may be activated by direct or indirect heating and/or pHadjustment to the optimum temperature and pH for the particular enzymeused. The enzyme may be inactivated by reducing the pH, adding aninhibiting salt, or increasing the temperature.

The water content during the conversion is affected by the productsolids, the condensation of injected steam used for direct heating, andmoisture evaporation during the conversion. The product solids areincreased by the hydrolysis. During conversion to a D.E. of 100, the dryweight of the starch is increased by 11.11% due to water covalentlybound to the hydrolysis reaction products. This dry weight increase isproportional to the degree of conversion. The solids are decreased dueto the condensed steam and increased by evaporation.

The powdered mixture of the starch, water, and enzyme does not requirestirring during the enzyme conversion step. In contrast to prior artenzyme conversion processes, the process is carried out at such a highsolids content that the mixture is a single phase.

Suitable starches can be derived from any source. Typical sources forthe starches are cereals, tubers, roots, legumes, fruit starches, andhybrid starches. Suitable native sources include corn, pea, potato,sweet potato, sorghum, wheat, rice, waxy maize, waxy tapioca, waxy rice,waxy barley, waxy wheat, waxy potato, waxy sorghum, and the like.

Using the unique high solids, single phase enzyme conversion process,one obtains a high solids maltodextrin syrup directly.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the molecular weight distributions of a non-convertedhydroxypropylated high amylose starch (Hylon VII) and an alphaamylase-converted high amylose starch (PO Hylon VII).

FIG. 2 shows the molecular weight distribution of a waxy maizeoctenylsuccinate enzyme converted using a mixture of alpha amylase andbeta amylase.

FIG. 3 shows the molecular weight distributions of fluidityhydroxypropylated waxy maize starches enzyme converted with a mixture ofalpha amylases (Sample No. 1) and a heat stable alpha amylase (SampleNo. 2).

FIG. 4 shows the molecular weight distributions of an alphaamylase-converted waxy maize (Sample No. 4) and an alphaamylase-converted waxy maize octenylsuccinate (Sample No. 5).

FIG. 5 shows the molecular weight profile of an alpha amylase-convertedhighly substituted waxy maize starch acetate (D.S. 1.05).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

There are other potential routes for preparing similar chemicallyderivatized maltodextrins. For example, a chemically derivatized starchcould be slurried in water, cooked to gelatinize and disperse thestarch, then enzyme converted with alpha amylase to yield a maltodextrinsyrup. There are several drawbacks to this process. First, the solidsduring the conversion will be limited by the viscosity of either theslurry or the dispersed, unconverted starch, whichever is higher.Second, enzyme activity at lower solids, probably 25 to 40%, will beless than at higher solids and, hence, to obtain comparable enzymeconversion to a D.E. in the maltodextrin range will require high enzymelevels and repeated doses at long conversion times. The claimed productsare at or near the limit of conversion for chemically derivatizedstarches having the desired degree of substitution. This difficultprocess will only yield similar products at lower solids. Anotherpotential process would be to slurry a native starch in water and thencook and enzyme convert as for conventional, commercial maltodextrins. Acommercial maltodextrin having the desired DE and molecular distributioncould then be chemically modified. This process, while producing a highsolids syrup, has other drawbacks. The by-products of the chemicalreaction, i.e., salts such as buffers, pH adjustments by-products,residual reagents, and reagent by-products, will be present in the finalsyrup limiting the syrup's use in food or products having indirect foodcontact such as envelope or packaging adhesives. Also, the distributionof the chemical substituents over the range of molecular weightcomponents in the maltodextrin will be different. Further, the chemicalderivatization of the maltodextrin tends to produce dark coloredproducts under alkaline conditions. Hydroxypropylated maltodextrins madeby this process are black.

Any starch is useful herein. Suitable starches include corn, pea,potato, sweet potato, sorghum, waxy maize, waxy tapioca, waxy rice, waxybarley, waxy potato, and waxy sorghum, and starches having amylosecontents of 40% or above (also referred to as high amylose starches).Preferred starches are waxy maize and corn.

It may be possible to convert chemically derivatized flours providedeffective enzyme levels are used to obtain the required conversion.

It may be possible to prepare enzyme-converted, chemically derivatizedmaltodextrins prepared from starches having an amylose content above 40%(commonly referred to as high amylose starches) by the high solids,single phase enzyme conversion process. In order to use these highamylose maltodextrins in adhesives, one would have to use them at lowersolids and the adhesives will need to be formulated with additionalpolyvinyl acetate and humectants to reduce the adhesive's initialviscosity. Further, additional ingredients such as glyoxal, alkalies, orsalts will be required to provide the adhesive with long term viscositystability. The use of humectants causes hygroscopic blocking. The use ofsalts such as nitrites, ureas, or chlorides also causes hygroscopicblocking.

Since high amylose starches are harder to gelatinize, it will also benecessary to use a higher level of chemical substitution to lower thestarch's gelatinization temperature. The increased substitution,however, inhibits the enzyme conversion.

Granular starches which have not been pregelatinized are preferred.Granular pregelatinized starches are also useful herein. Thepregelatinized granular starches are prepared by processes known in theart. The pregelatinization is carried out in such a way that a majorityof the starch granules are swollen, but remain intact. Exemplaryprocesses for preparing pregelatinized granular starches are disclosedin U.S. Pat. Nos. 4,280,851, 4,465,702, 5,037,929, and 5,149,799, thedisclosures of which are incorporated by reference. Predispersed (i.e.,pregelatinized starches) can also be used in the high solids, singlephase enzyme conversion process provided they are notcold-water-soluble. They can be prepared by jet-cooking andspray-drying.

Chemically derivatizing the starch can lower the gelatinizationtemperature and make it easier to carry out the conversion. The chemicalmodifications useful herein include heat- and/or acid-conversion,oxidation, phosphorylation, etherification, esterification, andconventional enzyme modification. These modifications are preferablyperformed before the starch is enzyme converted. Procedures forchemically modifying starches are described in the chapter "Starch andIts Modification" by M. W. Rutenberg, pages 22-26 to 22-47, Handbook ofWater Soluble Gums and Resins, R. L. Davidson, Editor (McGraw-Hill,Inc., New York, N.Y. 1980).

Physically modified starches, such as the thermally-inhibited starchesdescribed in WO 95/04082 (published Feb. 9, 1995), are also suitable foruse herein provided they have also been chemically modified.

Suitable enzymes for use herein include bacterial, fungal, plant, andanimal enzymes such as endo-alpha-amylases which cleave the 1→4glucosidic linkages of starch, beta-amylases which remove maltose unitsin a stepwise fashion from the non-reducing ends of thealpha-1→4-linkages, glucoamylases which remove glucose units in astepwise manner from the non-reducing end of starch molecules and cleaveboth the 1→4 and 1→6 linkages, and mixtures of the enzymes withdebranching enzymes such as isoamylase and pullulanese which cleave the1→6 glucosidic linkages of amylopectin-containing starches. Alphaamylases or mixtures thereof with other enzymes are preferred and areused for preparing the enzyme-converted, chemically derivatizedmaltodextrins having unique bimodal or polymodal molecular weightprofiles.

Enzymes can be purified by selective absorption or precipitation, butmany commercial products contain significant amounts of impurities inthe form of other enzymes, as well as in the form of inert protein. Forexample, commercial bacterial "amylases" will sometimes also contain"proteinases" (enzymes which break down protein). After extraction andpartial purification, commercial enzymes are sold either as powders oras liquid concentrates.

Process conditions for the use of a particular enzyme will vary and willusually be suggested by the supplier. The variables include temperature,pH, substrate solids concentration, enzyme dose, reaction time, and thepresence of activators. Very often there are no absolute optimumreaction conditions. The "optimum" pH may depend on temperature; the"optimum" temperature may depend on reaction time; the "optimum"reaction time may depend on cost, and so on. The reaction time can varyfrom 10 minutes to 24 hours or more, typically 1 to 4 hours for alphaamylase. The recommended conditions therefore are usually compromises.

The stability of an enzyme to adverse conditions is usually improved bythe presence of its substrate. Some enzymes are also stabilized bycertain salts (e.g., bacterial amylase is stabilized by calcium salts).It is necessary rigorously to exclude heavy metals and other enzymepoisons, such as oxidizing agents, from an enzyme reaction. Thesematerials usually result in permanent inactivation (i.e.,denaturization) of the enzyme. There are many instances however whereenzyme activity is reduced reversibly, frequently by the products of areaction (product inhibition) or by a substance which is structurallyrelated to the usual substrate (competitive inhibition). Reversibleinhibitors complex temporarily with the enzyme and therefore reduce theamount of enzyme available for the normal reaction.

Typical enzyme reaction conditions are discussed in "Technology of CornWet Milling" by P. H. Blanchard, Industrial Chemistry Library, Vol. 4(Elsevier, New York, N.Y. 1992).

Test Procedures Dextrose Equivalent

The dextrose equivalent (D.E.) is an indication of the degree ofconversion as shown by the reducing sugar content of the maltodextrin. AFehling Volumetric Method, as adapted from the Eynon-Lane VolumetricMethod #423 of the Cane Sugar Handbook by Spencer and Mead (John Wileyand Son Inc.), is used to determine the D.E.

A starch solution (w/v) of known concentration on an anhydrous starchbasis is prepared. The usual concentration is 10 g/200 ml. The starchsolution is transferred to a 50 ml/burette. To 50 ml of distilled waterin a 500 ml Erlenmeyer flask are added by pipette 5 ml each of FehlingSolutions A and B. Fehling Solution A contains 34.6 g of copper sulfate(CuSO₄.5H₂ O) dissolved in and brought to volume in a 500 ml volumetricflask. Fehling Solution B contains 173 g of Rochelle salt (NaKC₄ H₄O₆.4H₂ O) and 50 g of sodium hydroxide dissolved in and brought tovolume in a 500 ml volumetric flask. The Fehling Solutions arestandardized against Standardized Dextrose obtained from the Bureau ofStandards.

To determine the Fehling Factor, the test procedure is followed exceptthat 0.5000 anhydrous grams of dextrose per 200 ml of distilled water isused as the test solution. Using the following formula the factor isthen computed: ##EQU1## The factor applies to both Fehling solutions Aand B and is computed to 4 decimal places. The contents of the flask arebrought to a boil over a hot plate. The starch solution, while at aboil, is titrated to the distinctive reddish-brown colored end point(precipitated cuprous oxide complex). The ml of starch solution used isrecorded.

The D.E. is calculated using the following formula: ##EQU2## where thestarch solution equals the ml of starch solution used in the titrationto reach the end point and "starch concentration" equals theconcentration of the starch solution on an anhydrous basis expressed ing/ml.

Gel Permeation Chromatography (GPC)

Molecular weight (MW) distribution is determined using a WaterAssociates GPC-150C Model with a refractive index (RI) detector. Two PLgel columns (10⁵ and 10³ obtained from Polymer Laboratories of Amherst,Mass.) made of highly crosslinked spherical polystyrene/divinylbenzene,are connected in sequence. Dextrans from American Polymer StandardsCorp. (Mentor, Ohio) are used as the standards. The experimentalconditions are a column temperature of 80° C. and a flow rate of 1ml/min. The mobile phase is dimethyl sulfoxide (DMS) with 5 mM of sodiumnitrate (NaNO₃). The sample concentration is 0.1%. The injection volumeis 150

Brookfield Viscometer

Test samples are measured using a Model RVT Brookfield Viscometer andthe appropriate spindle which is selected based on the anticipatedviscosity of the material. The test sample is placed in position and thespindle is lowered into the sample to the appropriate height. Theviscometer is turned on and the spindle is rotated at a constant speed(e.g., 10 or 20 rpm) for at least 3 revolutions before a reading istaken. Using the appropriate conversion factors, the viscosity (incentipoises) of the sample is recorded.

EXAMPLES

In the examples which follow, non-pregelatinized granular starches areused unless it is otherwise stated and the various enzymes describedhereafter were used.

The alpha amylases were Ban 120 L and Termamyl. They were obtained fromNovo Nordisk. Ban 120 L is a conventional alpha amylase with an optimumtemperature of approximately 70° C., optimum pH of 6.0-6.5, an activityof 120 KNU/g, and recommended usage (based on the weight of the starch)of 0.005-1.0, preferably 0.01-0.5. Termamyl is a heat-stable alphaamylase with an optimum temperature greater than 90° C., an activity of120 KNU/g, and recommended usage (based on the weight of the starch) of0.005-1.0, preferably 0.01-0.5. One Kilo Novo unit (1 KNU) is the amountof enzyme which breaks down 5.26 g of starch (Merck, Amylum Solubile,Erg. B6, Batch 994 7275) per hour in Novo Nordisk's standard. Method fordetermining alpha amylase using soluble starch as the substrate, 0.0043Mcalcium content in solvent, 7-20 minutes at 37° C. and pH 5.6.

Example 1

This example shows the conversion of a chemically derivatized highamylose starch (70% amylose) using the high solids, single phase enzymeconversion process.

A hydroxypropylated high amylose starch (PO Hylon VII - D.S. 0.47) (1000g) was placed in a Ross Mixer with standard blades (Charles Ross & SonCo., Hauppauge, N.Y.). Sufficient water was added to give a total watercontent of 40%; 0.2% Termamyl was used. The starch was hydrolyzed at 98°C. for 4 hours, the starch was liquefied, and upon cooling the finalproduct was a viscous solution.

FIG. 1 shows the molecular weight distribution of the hydroxypropylatedHylon VII and the alpha amylase converted hydroxypropylated Hylon VII.

Example 2

This example shows the conversion of a waxy maize starch ester using thesingle phase, high solids enzyme conversion process.

A waxy maize octenylsuccinate, prepared by treatment withoctenylsuccinic anhydride (OSA), was treated with a mixture ofalpha-amylase and beta-amylase as described in Example 1, using 1,000 gof starch, 40% total water, and a mixture of 1.0 g of Ban 120 L and 0.5g of Spezyme. The mixture was held at 60° C. for 4 hours. A doughymaterial was formed. The product was broken up and air-dried. Part ofthe product (400 g) was slurried in 1,000 ml of water, adjusted to pH3.0 for 30 minutes with 0.1M hydrochloric acid, adjusted back to pH 6.0with 3% sodium hydroxide, and spray-dried.

The results show that when the OSA-treated waxy maize was converted witha mixture of alpha-amylase and beta-amylase, a low molecular weight peak(800) was observed (see FIG. 2). However, the low normalized area of thepeaks detected indicates that most of the sample is excluded and notdetected. The low molecular weight-material was estimated to be about12% based on the weight of the final product.

Example 3

This example describes a series of enzyme conversions run in a tengallon gate mixer reactor using Ban (B) and Termamyl (T), and mixturesthereof. The resulting maltodextrins were used in remoistenableadhesives.

Part A Preparation of Enzyme-Converted Chemically DerivatizedMaltodextrins

The internal dimensions of the tank were 16 inches tall by 16 inchesdiameter. The gate agitator, made from 1/2 inch wide by 2 inch deepstainless steel bar stock, had four vertical rakes 101/2 inches tall.The outside rakes cleared the inside tank wall by 1/2 inch; the insiderakes were 31/4 inches from the outside set. Attached to the tank topwere four breaker bars, of the same bar stock, located 13/4 and 51/4inches in from the tank wall. A electric drive, variable from 0 to 60rpm, powered the agitator. A vent in the tank top provided variabledraft forced exhaust. The tank sides and bottom were jacketed for steamheating or water cooling. A M inch diameter steam injection port wasprovided in the side wall 1 inch above the tank bottom. A thermocoupleprobe was attached to the bottom of one outside breaker bar. In the tankbottom a 2 inch port with a ball valve was provided for product drawoff. For these conversions a removable metal plug was inserted into thedraw port, flush with the tank bottom, to eliminate the possibility of aportion of the initial dry charge receiving non-uniform moisture,enzyme, or heat.

For each conversion 33 pounds of a commercially dry granular starch wasadded to the tank. The enzyme charge was diluted with sufficient waterto bring the charge to 25 percent moisture on an anhydrous basis. Thiswater/enzyme mix was added to the starch with mixing. The mixture, afteraddition of the enzyme/water mix, was a blend of dry starch and moiststarch aggregates less the one half inch in diameter.

At this point, the agitator is turned off for about 30 minutes to allowthe water to diffuse through out the starch. The starch, after thisrest, was a moist flowable powder.

The mixture was heated, generally by injection of live steam (at 32 psiexcept where indicated otherwise) into the mixture and/or optionally byheating the tank jacket. Typically, the mass was mixed during heating,but this was not required. Mixing only improved heat transfer.

As the granular starch gelatinized (or the cold-water-insolublepredispersed starch was solubilized), it was converted and the reactionmixture changed from a moist powder to a wet doughy mass and then to adispersed syrup. These changes occurred as the temperature was increasedfrom 50° C. to 90° C. The temperature at which the onset of liquefactionoccurred varied depending on the water activity, enzyme activationtemperature, and starch type.

In this vented tank, there was some loss of moisture during the fullheating cycle. When the injection steam was shut off, the temperaturewas maintained at the indicated temperature with jacket heating for 30minutes. The batch was then cooled to less than 50° C. and drawn off.Optionally, the pH was reduced to 3.5 with phosphoric and the mixturewas held for 30 minutes to deactivate any residual enzyme. The pH wasreadjusted if required.

To 43.52 parts of the indicated starch were added a mixture of 6.95parts water and the indicated amount of Ban 120 L and/or Termamyl. Thegate mixer was at 30 rpm while the premix was slowly added in steadystream. Mixing was continued until the starch was uniformly damp. Theagitator was shut down and the mixture was heated with live steam andjacketed steam to 82°-93° C. (180°-200° F.) for 30 minutes. Then 6.94parts of water were added.

The mixer was restarted and agitation was continued at 30 rpm while themixture was being heated at 93°-99° C. (200°-210° F.). When the adhesiveproduct clarified and was smooth, the viscosity and solids were tested.After the test results were recorded, the pH was adjusted to 3.5 with85% phosphoric acid, and additional acid added, if needed, to end theenzyme activity.

The starch base used, enzyme and amount used, and properties of theresulting suitable and comparative maltodextrins (solids, D.E., andD.S.) are summarized in Table 1. The three month viscosity stability ofthe same maltodextrins is reported in Table 2. The GPC molecular weightprofiles of Sample Nos. 1 and 2 are shown in FIG. 3 and of Sample Nos. 4and 5 are shown in FIG. 4.

                  TABLE 1                                                         ______________________________________                                                          Maltodextrin                                                No.   Starch        Enzyme  Solids  D.E. D.S.                                 ______________________________________                                        1*    35 WF,        0.045 B 62.2    13.7 0.16                                       Hydroxypropylated                                                                           0.045 T                                                         Waxy Maize                                                              2     35 WF,        0.09 T  70.9    11.0 0.16                                       Hydroxypropylated                                                             Waxy Maize                                                              3     35 WF,        0.18 T  62.8    10.6 0.16                                       Hydroxypropylated                                                             Waxy Maize                                                              4     Hydroxypropylated                                                                           0.09 T  68.9    13.2 0.09                                       Waxy Maize                                                              5     Octenyl-succinate                                                                           0.09 T  60.2    15.2 0.02                                       Waxy Maize                                                              6**   35 WF,        0.045 T 60.0     7.4 0.16                                       Hydroxypropylated                                                                           0.045 T                                                         Waxy Maize                                                              7     35 WF,        0.09 T  69.0         0.16                                       Hydroxypropylated                                                             Waxy Maize                                                              ______________________________________                                         *For Sample No. 1, the steam pressure was 8 psi.                              **For Sample No. 6, the enzyme addition was carried out in two steps.    

Example 4

This example shows the preparation of an enzyme-converted, highlyacetylated starch which is characterized by its water dispersibility. Itwas prepared using the single phase, high solids process.

Part A

Waxy maize was acetylated using the procedure of U.S. Pat. No.5,321,132, discussed previously. The starch solids were 40% (as is), thepH 8.5, the temperature 25° C, and reaction time 4 hours. The granularstarches (1.05 D.S.) were recovered by filtering, washing to less than500 micromhos conductivity, and air drying to 10% moisture.

Part B

The water-insoluble acetylated waxy maize starch (1.05 D.S.) wasconverted by alpha amylase, as described above, using 1,000 g starch,40% total water, and 1 ml each of Ban 120L and Termamyl. The starchbegan to liquify at about 80° C. A watery liquid product was observed inthe Ross Mixer as the temperature increased to 95°-98° C. After themixture was held at 95°-98° C. for 2 hours, a hardened, rock-likematerial formed in the Ross mixer.

The unconverted acetylated waxy maize (1.05 D.S.) cannot be detected byGPC, probably because of its high molecular weight or great hydrodynamicvolume in the DMSO mobile phase. The GPC molecular weight profile ofthis converted acetylated waxy maize (1.05 D.S.) showed multiple peaks(see FIG. 5). Its Brookfield viscosity (5% solids in DMSO, Spindle #1,100 rpm) was 56 cps, whereas the Brookfield viscosity of thenon-converted acetylated waxy maize at the same concentration was 2,480cps (5% solids, Spindle #4, 20 rpm). This significant viscosityreduction indicates that the acetylated waxy maize has been hydrolyzedand depolymerized even though it had a DS of 1.05.

Part C

A 3.4 gram sample of the above enzyme-converted intermediate D.S.acetylated waxy maize was dispersed in 96 grams of distilled water atroom temperature with mixing provided by a magnetic stirrer. Within afew minutes, the sample had dispersed into a milky white dispersion. Asmall portion settled out over several hours. The remaining dispersionwas stable for three days at room temperature. The dispersed cloudyproduct turned into a clear solution when propanol or ethanol was added.The high alcohol solubility indicates that the enzyme-converted productstill contains a high degree of acetate substitution.

This demonstrates the utility of the enzyme converted, intermediate D.S.acetylated waxy maize prepared by the high solids, single phase processin application areas where the converted starch will be added as anaqueous emulsion.

Now that the preferred embodiments of the invention have been describedin detail, various modifications and improvements thereon will becomereadily apparent to those skilled in the art. Accordingly, the spiritand scope of the present invention are to be limited only by theappended claims and not by the following specification.

What is claimed:
 1. A maltodextrin syrup containing a chemicallyderivatized maltodextrin, which syrup after enzyme conversion of achemically derivatized starch and prior to concentration, has a solidscontent of at least 55% by weight and which maltodextrin has (i)substituents in an amount sufficient to provide a degree of substitutionof about 0.01 to less than about 0.50; (ii) a reducing sugar content ofbetween about 5 and about 19 dextrose equivalent; and (iii) a polymodalmolecular weight distribution having one peak between about 630 to about1600 daltons and at least one other peak between about 1600 and about2,500,000 daltons.
 2. The maltodextrin syrup of claim 1, wherein themaltodextrin is from a cereal, tuber, root, legume, or fruit starch. 3.The maltodextrin syrup of claim 2, wherein the substituents are esterand/or ether groups.
 4. The maltodextrin syrup of claim 3, wherein thestarch is selected from the group consisting of corn, pea, potato, sweetpotato, sorghum, waxy maize, waxy tapioca, waxy rice, waxy barley, waxypotato, and waxy sorghum; and wherein the degree of substitution isabout 0.05 to about 0.17 and where the ether group substituents arehydroxyalkyl groups and the ester group substituents are succinate,octenylsuccinate, or acetate groups.
 5. The maltodextrin syrup of claim2, wherein the chemically-derivatized maltodextrin is prepared from aderivatized starch having a degree of substitution of about 0.05 andabout 0.17; wherein the dextrose equivalent is between about 10 andabout 17; wherein the other peak(s) are between about 1600 and about160,000 daltons; and wherein the solids content of the maltodextrinsyrup is greater than about 60% by weight.
 6. The maltodextrin syrup ofclaim 5, wherein the solids content of the resulting maltodextrin syrupis about 65 to about 75% by weight and wherein the derivatized starch isa derivatized corn starch or a derivatized waxy maize starch.
 7. Themaltodextrin syrup of claim 6, wherein the degree of substitution isbetween about 0.05 and about 0.17 and the dextrose equivalent is betweenabout 10 and about
 17. 8. A maltodextrin syrup containing a chemicallyderivatized maltodextrin, which syrup is prepared by the steps of:(a)adding, to a chemically derivatized starch having substituents in anamount sufficient to provide a degree of substitution of about 0.01 toabout 0.50, an alpha amylase enzyme or an enzyme mixture containing analpha amylase enzyme, and water in an amount sufficient to produce asingle phase powdered mixture without a visible free water phase; (b)activating the alpha amylase enzyme by heating the powdered mixture toan optimum temperature for the alpha amylase enzyme; and (c) allowingthe chemically derivatized starch to hydrolyze to a degree sufficient togive the chemically derivatized maltodextrin having a reducing sugarcontent of between about 5 and about 19 and the syrup having a solidscontent of at least 55% by weight.
 9. The maltodextrin syrup of claim 8,wherein the chemically derivatized starch is prepared from an unmodifiedor modified starch.
 10. The maltodextrin syrup of claim 9, wherein thechemically derivatized starch is prepared by reacting a starch with anetherifying reagent selected from the group consisting of ethyleneoxide, propylene oxide, diethylaminoethyl chloride hydrochloride, and3-chloro-2-hydroxypropyl trimethylammonium chloride, or with anesterifying reagent selected from the group consisting of succinicanhydride, octenylsuccinic anhydride, and acetic anhydride, and mixturesthereof.
 11. The maltodextrin syrup of claim 8, wherein the pH of thepowdered mixture is adjusted to the optimum pH for the alpha amylase.12. The maltodextrin syrup of claim 11, wherein the alpha amylase is abacterial alpha amylase and the optimum temperature is about 77 to about85° C. and the optimum pH is about 5.8 to about 6.2; or wherein thealpha amylase is a high temperature alpha amylase and the optimumtemperature is about 95 to about 105° C. and the optimum pH is about 6.0to about 6.5.
 13. The maltodextrin of claim 8, wherein the alpha amylaseis inactivated after the desired dextrose equivalent is reached byraising the temperature, lowering the pH, and/or adding an inhibitingsalt.
 14. The maltodextrin syrup of claim 8, wherein the alpha amylaseis used in combination with a beta amylase and/or a glucoamylase. 15.The maltodextrin syrup of claim 8, further comprising a step (d) ofremoving the water from the aqueous maltodextrin syrup and recovering apowdered chemically derivatized maltodextrin.